文献类型：期刊文献

英文题名：Regulating π-Conjugation in sp2-Carbon-Linked Covalent Organic Frameworks for Efficient Metal-Free CO2 Photoreduction with H2O

作者：Yang, Lan[1];Yan, Wenkai[2];Yang, Na[3];Wang, Guofeng[3];Bi, Yingpu[2];Tian, Chengcheng[4];Liu, Honglai[1];Zhu, Xiang[3]

机构：[1]East China Univ Sci & Technol, Sch Chem & Mol Engn, State Key Lab Chem Engn, Shanghai 200237, Peoples R China;[2]Chinese Acad Sci, Lanzhou Inst Chem Phys, Natl Engn Res Ctr Fine Petrochem Intermediates, State Key Lab Oxo Synth & Select Oxidat, Lanzhou 730000, Peoples R China;[3]Chinese Acad Sci, Suzhou Res Inst, State Key Lab Oxo Synth & Select Oxidat, Lanzhou Inst Chem Phys, R China, Suzhou 215000, Peoples R China;[4]East China Univ Sci & Technol, Sch Resources & Environm Engn, Shanghai 200237, Peoples R China

年份：2023

卷号：19

期号：27

外文期刊名：SMALL

收录：;EI(收录号：20231313817075);WOS:【SCI-EXPANDED(收录号:WOS:000958686700001)】；

基金：L.Y. and W.Y. contributed equally to this work. X.Z. thanks the financial support from the National Program for Young Talents of China, Foundation research project of Jiangsu Province (Y91266JZQ1), National Natural Science Foundation of China (E00966GZQ2 and E00966GMS1). C.T. was supported by Shanghai International Science and Technology Cooperation Project (20230710700) and the National Natural Science Foundation of China (52170109). H.L. was supported by the Fundamental Research Funds for the Central Universities (2022ZFJH004).

语种：英文

外文关键词：ethynyl linkages; photocatalytic CO2 reduction; sp(2)-carbon-linked covalent organic frameworks; pi-conjugation

摘要：The development of sp(2)-carbon-linked covalent organic frameworks (sp(2)c-COFs) as artificial photocatalysts for solar-driven conversion of CO2 into chemical feedstock has captured growing attention, but catalytic performance has been significantly limited by their intrinsic organic linkages. Here, a simple, yet efficient approach is reported to improve the CO2 photoreduction on metal-free sp(2)c-COFs by rationally regulating their intrinsic pi-conjugation. The incorporation of ethynyl groups into conjugated skeletons affords a significant improvement in pi-conjugation and facilitates the photogenerated charge separation and transfer, thereby boosting the CO2 photoreduction in a solid-gas mode with only water vapor and CO2. The resultant CO production rate reaches as high as 382.0 mu mol g(-1) h(-1), ranking at the top among all additive-free CO2 photoreduction catalysts. The simple modulation approach not only enables to achieve enhanced CO2 reduction performance but also simultaneously gives a rise to extend the understanding of structure-property relationship and offer new possibilities for the development of new pi-conjugated COF-based artificial photocatalysts.